US20240376559A1 - Method for producing slag having a desired quality - Google Patents
Method for producing slag having a desired quality Download PDFInfo
- Publication number
- US20240376559A1 US20240376559A1 US18/286,474 US202218286474A US2024376559A1 US 20240376559 A1 US20240376559 A1 US 20240376559A1 US 202218286474 A US202218286474 A US 202218286474A US 2024376559 A1 US2024376559 A1 US 2024376559A1
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- US
- United States
- Prior art keywords
- slag
- iron
- reactor
- additive
- containing intermediate
- Prior art date
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- 239000002893 slag Substances 0.000 title claims abstract description 168
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 152
- 229910052742 iron Inorganic materials 0.000 claims description 76
- 239000000654 additive Substances 0.000 claims description 51
- 230000000996 additive effect Effects 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 38
- 230000009467 reduction Effects 0.000 claims description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000004566 building material Substances 0.000 claims description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- 239000004568 cement Substances 0.000 claims description 15
- 238000007669 thermal treatment Methods 0.000 claims description 14
- 229910000805 Pig iron Inorganic materials 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000000704 physical effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000003723 Smelting Methods 0.000 description 34
- 239000000543 intermediate Substances 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000004576 sand Substances 0.000 description 20
- 235000013980 iron oxide Nutrition 0.000 description 14
- 238000010079 rubber tapping Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000428 dust Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 239000011398 Portland cement Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000009847 ladle furnace Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/04—Making slag of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
- C21B3/06—Treatment of liquid slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
- C21B13/143—Injection of partially reduced ore into a molten bath
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2300/00—Process aspects
- C21B2300/02—Particular sequence of the process steps
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2300/00—Process aspects
- C21B2300/04—Modeling of the process, e.g. for control purposes; CII
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2400/00—Treatment of slags originating from iron or steel processes
- C21B2400/02—Physical or chemical treatment of slags
Definitions
- the invention pertains to a method for generating slag and for making controlled adjustments to its characteristics, for use as mineral building material, for example.
- the characteristics of the slag encompass the physical and chemical composition and also the mineralogical properties of the slag.
- iron is present only in the form of iron oxide.
- Pig iron is produced, for example, in blast furnaces. These are shaft furnaces operating on the countercurrent principle, where the charge—that is, lump ore, pellets or sinter together with coke as reducing agent and limestone and possibly further additives—is fed in at the top side and a flow of hot gases is passed through this charge from the bottom side. In this way, the feed material is steadily heated during the transient time.
- the substoichiometric combustion of the coke results in the formation of the reduction-capable gas carbon monoxide (CO), which reduces the iron oxides contained in the charge into iron; the CO may oxidize to carbon dioxide (CO2) in the process. Because of the temperatures prevailing at the bottom of the blast furnace, the iron is present in the liquid state.
- CO carbon monoxide
- pig iron and slag are tapped off at periodic intervals. Rapid cooling of the smelting furnace slag, possibly leading to a glassy solidification, can be used to produce slag sand. Sand properties can be positively influenced by the milling-in of cement. Furthermore, by substituting the slag sand for cement clinker, the CO 2 footprint of cement can be improved as well.
- composition of the slag here is dictated substantially by the gangue in the iron ore, the limestone fraction, and secondary constituents and additives in the feed material.
- EP 1 354 969 B1 and EP 632 791 B1 show methods for admixing the slag post-tapping with additives to optimize the composition of the slag for the slag sand.
- the disadvantage of this method is that the addition of the additives may cause the slag to cool down more quickly, so making it no longer possible for the additives to bind optimally with the slag.
- the greater the amount of additives admixed to the slag the more rapid the cooling of the slag.
- a skewed composition of the slag may arise, with an accumulation of the additives in one region and a deficiency of the additives in another region.
- DE 197 08 034 A1 discloses a method for producing liquid pig iron or liquid steel precursors.
- EP 1 198 599 B1 discloses a method for slag conditioning with introduction of smelting residues.
- EP 1 627 084 B1 discloses a method for profitably utilizing slag.
- DE 103 40 880 A1 discloses a method and an apparatus for atomizing slag.
- DE 10 2020 205 493 A1 discloses a method for establishing a controlled slag phase in a smelting assembly.
- direct reduction plants and electric arc furnaces/smelters are also known in principle. Not known, however, is an analysis of the slag and/or the intermediates for the purpose of optimized adjustment of the slag characteristics.
- the object of the present invention is to create an improved concept for a method for generating slag and for adjusting the characteristics of the slag arising in the smelting furnace.
- a method for generating slag of desired characteristics in the production of pig iron with steps as follows: a) heating iron oxide in a first reactor, so that with a reducing agent present a majority of the iron oxide is reduced to iron and an iron-containing intermediate is formed. This is done using a direct reduction plant. As the end product of the direct reduction plant, the iron-containing intermediate is then present, and may also be referred to as sponge iron.
- the iron-containing intermediate is heated in a second reactor, to give pig iron and the slag.
- the heating takes place preferably in a smelter in a reducing atmosphere.
- step c) In a further step, which may also take place before or parallel to step b), the iron-containing intermediate and/or the slag which is deposited during the further heating of the iron-containing intermediate are/is analyzed.
- the iron-containing intermediate is taken for analysis at the end of the direct reduction plant, between direct reduction plant and smelter (i.e., in both cases, before the heating in the smelter) or in the smelter (i.e., during the heating). Additionally or alternatively, a sample of the slag heated to the final temperature may also be taken from the smelter.
- a property of an additive to be added to the iron-containing intermediate is determined in order to alter the composition of the slag.
- a sample is taken of the iron-containing intermediate and/or of the slag. Since in the iron-containing intermediate, the iron oxide is already present in a very far-reduced state, the characteristics of the later slag can already be determined very well from it.
- the analysis reflects the actual state of the slag.
- the intermediate may comprise, for example, pyrites, dolomite, ilmenite or bauxite, or the basic form of the oxidic compounds, or any desired combination of the stated substances. These substances are also referred to as adjuvants and they influence the properties of the slag.
- the slag it is advantageous for the slag to have good reception capability for extraneous substances, to have a suitable velocity (preferably between 1.05 Pa*s and 1.15 Pa*s (pascal times second)) and to have a temperature at which, as a result of the solidification, the slag breaks down into the appropriate particle size fraction and there is sufficient formation of glassy phase, and to have good binding capacity for cement production.
- the good reception capacity of the slag ensures effective reception of the additives and hence high homogeneity of the slag.
- the viscosity enables the slag to flow through the tapping hole.
- the temperature/the composition and also the binding capacity are relevant to the quality of the end product—for example, slag sand, Portland cement, or similar.
- the additive thus determined is introduced into the second reactor, such as the smelter, for example, during the heating of the slag, to give the slag of the desired characteristics.
- the desired characteristics are also referred to as target characteristics.
- a control unit may recognize from the analysis that the slag requires a thermal treatment to give the slag having the desired characteristics, and may initiate the thermal treatment.
- the liquid metal and the slag can be tapped off through tapping holes in the smelter. After the slag has exited the tapping hole, it is quenched, preferably with water, and atomized and therefore granulated. The aim is to obtain more than 90% glassy solidification. After that, the granules are ready for further use. As a check, and in order to be able to correct any faulty assumptions, the final granules may also be analyzed to ascertain whether they have the desired properties.
- a thermal treatment of the slag may also be derived, in particular a defined cooling rate to give the desired property of the slag.
- a smelting furnace for the generation of pig iron and slag having desired characteristics.
- the smelting furnace comprises a direct reduction plant which is configured to heat iron oxide so that with a reducing agent present a majority of the iron oxide is reduced to iron and an iron-containing intermediate is formed.
- the iron oxide is heated, for example, to a temperature of between 900° C. and 1100° C.
- the reducing agent preferably hydrogen, which may be recovered, for example, from the electrolysis of water using regenerative energies (wind, water, solar) for the provision of the required power, for reducing CO 2 emissions, may be heated to the necessary reaction temperature for the operation of the direct reduction plant, before being introduced into the direct reduction plant.
- the iron-containing intermediate is also referred to as sponge iron.
- the reactor arrangement Downstream of the direct reduction plant is a reactor arrangement.
- the reactor arrangement receives the iron-containing intermediate and heats it to give pig iron and slag.
- the reactor arrangement may comprise one reactor or a plurality of reactors.
- the reactor, or one reactor of the plurality of reactors, for heating the iron-containing intermediate may be an electric arc furnace or a smelter or an induction furnace.
- An electric arc furnace is an electrical furnace which heats a substance in an oxidizing atmosphere, typically discontinuously. Discontinuously means that a quantity of the substance is heated and the substance after the heating is withdrawn before a new amount of the substance is heated.
- a smelter is an electric furnace which heats a substance in a reducing atmosphere, typically continuously. Continuously means that a portion of the substance in the smelter is tapped off regularly, while the smelter is fed to new substance.
- iron-containing intermediate is introduced into the smelter and, likewise regularly, portions of the pig iron and of the slag are tapped off.
- a smelter for example, a residual melt may be left which may be seen in turn as a starting point for the smelting of further substance.
- the smelter is also referred to as a melting-reduction furnace, low-shaft furnace or submerged arc furnace (SAF).
- SAF submerged arc furnace
- terms such as open slag bath furnace (OSBF) are also customary.
- the temperature up to which the heating takes place is, for example, 1500° C. to 1600° C. if the slag is being used to produce slag sand. This is the temperature at which the slag is tapped off.
- the maximum slag temperature may also be higher, since in this case the eutectic of the slag is no longer attained.
- the temperature at which the iron is tapped off is somewhat lower and is, for example, between 1400° C. and 1500° C. In particular, therefore, the tapping temperature of the pig iron is, for example, between 80° C. and 120° C. lower than the tapping temperature of the slag.
- the atmosphere, more particularly reducing atmosphere, in the smelter is obtained, for example, by the reaction of carbon, dissolved in sufficient quantity in the melt, with oxidic constituents of the intermediate, owing to the prevailing chemical/physical conditions, to give a reducing gas, for example. If carbon is not present in sufficient amount in the melt, this reducing atmosphere may be generated by supplying a reduction gas and/or reduction gas-forming substance.
- the smelting furnace further comprises an analysis unit which is configured to analyze the iron-containing intermediate and/or the slag.
- the analyzing may take place during tapping or by sampling before the tapping, or in situ.
- the analyzing may preferably take place online.
- the slag may be determined for the production of mineral building materials, such as for the production of slag sand or Portland cement, for example, by analysis of the concentration ratio of calcium, silicon, aluminum and iron.
- the mineral building materials may differ in their composition and in their properties from slag sand.
- the mineral building material may differ in its chemical and/or physical and/or mineralogical properties from conventional slag sand.
- the analysis unit may be a laboratory located in the vicinity of the smelting furnace, for the laboratory results to be utilized for rapid influencing of the product, in particular.
- the smelting furnace has a control unit which is configured, depending on an analytical result, to determine a property of the added additive so as to alter a composition of the slag (actual composition) and to obtain the slag with a desired composition (target composition). Additionally or alternatively, the control unit may also recognize whether the slag requires a thermal treatment to obtain the slag having the desired characteristics.
- the additive is understood to refer in particular to a mixture of different substances.
- Substances used may include pyrites, dolomite, ilmenite and bauxite.
- the selection of the substances is then regarded as a property of the additive.
- the fraction of the selected substances within the total amount of the additive may be viewed as a property of the additive.
- the total amount of the additive or the amount of the selected substances may also be viewed as a property of the additive.
- the amount denotes the mass or the volume of the substance.
- the property of the additive encompasses not only the selection of the substances but also their respective fractions, i.e., the composition of the additive, and also the amount of the additive.
- the thermal treatment may arise from the analysis of the actual state of the slag or else the desired characteristics of the slag.
- the thermal treatment is, for example, the operation of a defined temperature curve of the reactor arrangement for heating or else cooling the slag.
- a defined temperature curve of the reactor arrangement for heating or else cooling the slag.
- Different mineral building materials may have different requirements with regard to a temperature profile.
- a further possibility for control or regulation, as well as the adding of the additive is to introduce heat into the reactor arrangement or else remove heat in a target-oriented manner on the basis of the measurement results obtained using the analysis unit.
- This supply or removal of heat may be variable over time—that is, it may have the goal, for example, of pursuing a temperature profile for slag and/or melt that necessitates a supply of heat at certain times and a removal of heat at other times, and the leaving of the process to itself, in thermal terms, at still other times.
- a goal temperature for slag and/or melt in order to influence properties of slag and/or melt in a goal-directed way.
- the properties of slags and melts may be influenced not only by individual temperatures but also by the traversal of temperature profiles in order to obtain or to avoid particular material phases.
- the desired characteristics for the slag are the characteristics whereby a mineral building material, formed after the granulation of the slag, has a desired chemical composition and/or a desired physical property and/or a mineralogical property.
- granulation encompasses, for example, the rapid cooling (quenching) and atomization of the slag after tapping.
- a different thermal treatment may occur in order to obtain the granules.
- the desired characteristics of the slag especially in terms of mineralogical phase formation, elution behavior, etc., may accordingly be selected such as to form, for example, slag sand or Portland cement or any other mineral building material.
- the smelting furnace disclosed is a response to the concern that the current efforts to replace coke by hydrogen as a reducing agent, owing to the high CO 2 emissions in steelmaking, mean that, as a result of the switchover to the direct reduction process, the production of slag sand will be lost—such production in Germany alone accounts annularly for around six million metric tons.
- the smelting furnace described, more specifically the first reactor is therefore already designed for the direct reduction process as well, and can be operated with (natural) gas or, advantageously, with hydrogen as reducing agent. It also enables the smelting furnace to produce mineralogical building materials other than the conventional slag sand, as well.
- the idea is to use a direct reduction plant and a reactor arrangement with, for example, a smelter.
- the iron oxide is reduced via direct reduction methods.
- the iron can then be present at the end of the direct reduction plant as an iron-containing intermediate in solid form, in the form of sponge iron, for example.
- the smelter for example, the iron-containing intermediate is then heated to the preset temperature at which the liquid iron is tapped off.
- the analysis there are diverse possibilities, which are described illustratively on the basis of the smelter as (part of) the reactor arrangement.
- the heating for example, no further iron-containing intermediate is added to the reactor arrangement, more particularly to the smelter.
- the characteristics of the future slag may be ascertained via analysis of the iron-containing intermediate. From this it is possible to ascertain for example, what physical composition the additive should have and what amount of the additive should be added to the reactor arrangement in order to obtain desired characteristics for the slag.
- the additive may also be determined on the basis of the analysis of the iron-containing intermediate. In other words, only the characteristics of the newly arrived slag fraction need be adjusted. Furthermore, however, for verification, it is also possible to determine the characteristics of the slag in the smelter and, in the event of deviations from the desired characteristics, to adapt them by addition of the additive.
- the analysis unit can determine actual characteristics of the iron-containing intermediate and/or the slag and compare them with desired target characteristics of the slag, and adjust the properties of the additive or the thermal treatment depending on the difference between actual composition and target composition.
- the additives are heated with the iron-containing intermediate and may therefore mix or bind fully with or to the slag.
- the result is a uniform slag having the desired characteristics.
- the reactor arrangement comprises a first reactor, preferably the smelter, and a second reactor.
- the first reactor receives the iron-containing intermediate and heats it, to give the iron and the slag.
- the second reactor receives the liquid slag and subjects it via the control unit to a further treatment, to give the desired characteristics of the slag.
- the further treatment by the control unit has already been comprehensively described and comprises the addition of the additive, adjusted in terms of its properties.
- the further treatment comprises a thermal treatment of the slag. In this case, the slag is adjusted to the desired characteristics only after the iron has been tapped off, so that the process of pig iron production does not need to be altered.
- the reactor arrangement preferably the first reactor or the smelter, has an opening for introducing raw material, especially furnace dust, into the reactor unit.
- raw material especially furnace dust
- the furnace dust swelled up and captured in the direct reduction plant may be introduced, or else any other raw materials, especially those which can be airborne.
- These raw materials need not necessarily be attained in production of iron; instead, raw materials (with the capacity to be airborne) from other industries, such as from clay production, for example, may also be added.
- the raw material may be processed, for example dried and/or granulated, before being introduced into the reactor arrangement. The characteristics of the slag are altered as a result and are analyzed by the analysis unit after the raw material has been added.
- furnace dust contains a not inconsiderable fraction of bound iron (in the lower single-digit percentage range) which is currently lost in production of iron.
- the iron it contains is likewise melted and is therefore not lost.
- any desired raw material may also, generally, be introduced into the reactor arrangement. If the raw material is too small, it may be granulated for greater ease of introduction into the reactor arrangement. The granulation or pelletizing of raw material is advantageous if it has airborne capability.
- a material is regarded as having airborne capability if its particle size is less than 5 mm, preferably less than 3 mm or less than 1.5 mm.
- Raw materials with airborne capability can also be introduced into the reactor arrangement, but only by means of a carrier gas, which, however, is typically unwanted in the reactor arrangement.
- a further advantage of the method is the use also of fine-grain feedstocks (raw material) in the new process.
- fine-grain feedstocks are carried by the gas stream in the bed material and so do not enter the melt. Accordingly, this dust is lost to production.
- the dust it is now possible, with circumvension of traversal through the upper part of the process, for the dust to be introduced directly into the smelting furnace, optionally mixed with other substances and/or already generally pretreated—for example, but not exclusively, by means of heat, comminution or agglomeration.
- control unit is configured to select the amount of the additive such that the slag has a basicity of 1 to 5.5, preferably of 1.13 to 2. This is advantageous for the generation of mineral building materials.
- the second reactor is configured to atomize the slag to give atomized slag, the atomized slag having a particle size of 1 to 100 ⁇ m, preferably 1 to 40 ⁇ m.
- the atomizing enables rapid cooling of the slag, in order to obtain the required glassy solidification for production of slag sand, for example.
- the atomizing may take place in the second reactor as part of the thermal treatment.
- the second reactor generates a mineral building material, a binder for example. It is possible, for example, for the control unit, as the additive or as part of the additive, to introduce cement into the second reactor, the second reactor being configured to mix the atomized slag and the cement with one another, with the atomized slag being mixed with cement in a ratio of 36:64 to 95:5, preferably 60:40 to 80:20, to give the mineral building material having a 28-d standard strength of at least 30 N/mm 2 .
- FIG. 1 contrasts the conventional blast furnace ( FIG. 1 a ) with an exemplary embodiment of the smelting furnace ( FIG. 1 b ), in each case in a schematic sectional representation;
- FIG. 2 shows an exemplary embodiment of the smelting furnace from FIG. 1 b;
- FIG. 3 shows a further exemplary embodiment of the smelting furnace from FIG. 1 b , which can also be combined with the exemplary embodiment from FIG. 2 ;
- FIG. 4 shows a schematic representation of a ternary diagram of the principal constituents of the slag for the cement industry.
- FIG. 1 contrasts a conventional blast furnace 20 a ( FIG. 1 a ) with a smelting furnace 20 b ( FIG. 1 b ) which comprises a direct reduction plant 21 a and a reactor arrangement 21 b, represented here as a smelter. Both plants each have a material feed 22 a, 22 b, through which components including the iron oxide to be smelted enter the blast furnace. In the case of the blast furnace, the coke may also be added via this route.
- the smelting process is divided into different zones. A preheating zone 24 a, 24 b is followed by a reduction zone 26 a, 26 b, in which the major part of the reduction of the iron oxide to iron takes place.
- the carbonizing zone 28 a, 28 b a portion of the iron becomes enriched with carbon.
- the zones described so far are located in the direct reduction plant 21 a of the smelting furnace. Below the carbonizing zone in the blast furnace, and in the smelter in the smelting furnace, there is also the smelting zone, in which the temperature is high enough for the iron to liquefy and separate from the likewise liquid slag.
- the liquid iron and the liquid slag may be withdrawn through tapping holes 32 a, 32 b, 32 b ′.
- the blast furnace 20 a additionally has a feed 34 for hot blasts, while the direct reduction plant 21 a has a feed 36 a, 36 b for a reduction gas, hydrogen or carbon monoxide for example.
- the smelter 21 b comprises a main opening 38 , through which an iron-containing intermediate 39 passes from the direct reduction plant into the smelter 21 b.
- the smelter 21 b additionally comprises an opening 40 , through which an additive can be introduced into the smelter. If the additive is to contain different substances, there may be one opening provided per substance. Alternatively, the substances may be mixed beforehand to give the additive, and then enter the smelter through an opening in the form of a mixed additive.
- the smelter 21 b On the bottom of the smelter, furthermore, there is a pool of slag 42 and iron 44 .
- the openings are advantageously designed such that the smelter 21 b carries out the heating in the absence of air. This means that the direct reduction plant can be connected securely to the smelter so that the iron-containing intermediate enters the smelter without air contact.
- the smelter is a separate assembly from the direct reduction plant, it is now possible, in contrast to the blast furnace, to withdraw a sample of the slag and/or of the iron-containing intermediate 39 directly in the smelter before the withdrawal of the slag. Alternatively, the sample may even be taken from the direct reduction plant itself.
- the sample can be analyzed for its characteristics in an analysis unit 43 .
- a control unit 45 ascertains the quality of the additive. Via signal line 51 a, the control unit is able to produce the additive and introduce it into the reactor arrangement, more particularly the smelter. Additionally or alternatively, the control unit 45 may also, via a further signal line 51 a, set a temperature of the smelter. It is thus possible to carry out thermal treatment of the melt by operation of a predetermined temperature curve, for example.
- the smelting furnace 20 b has the advantage, in contrast to a direct reduction plant in combination with an electric arc furnace operating under an oxidizing atmosphere, for example, that the further processing operation of an iron works attached to the blast furnace can also be used for the smelting furnace.
- the iron can be refined into steel in a converter.
- the liquid steel may be desulfurized in a ladle furnace and adjusted in its quality and then shaped by means of a continuous casting plant.
- FIG. 2 shows the representation of the smelting furnace 20 b from FIG. 1 b in an exemplary embodiment.
- the exemplary embodiment additionally comprises a feed 52 for raw material into the smelter.
- the feed 52 may be configured as a return conduit 52 a from the direct reduction furnace 21 a, to pass the raw material from the direct reduction furnace into the smelter. If the raw material is not directly suitable for being introduced into the smelter, it is also possible for it to be subjected to an aftertreatment beforehand.
- the blown introduction of the reduction gas has the effect in particular of swirling up furnace dust. This dust can be captured and optionally preprocessed (e.g., pressed to form pellets or filtered) and passed into the smelter.
- the feed comprises an external feed 52 b for raw material.
- furnace dust collected on the iron works site, or else raw material from other industries can be introduced into the smelter.
- FIG. 3 shows an alternative exemplary embodiment of the smelting furnace 20 b from FIG. 1 b .
- the reactor arrangement 21 b has a two-stage construction.
- a first reactor 54 a presently the smelter, already shown in FIG. 1 b and FIG. 2 , is supplemented by a second reactor 54 b.
- the second reactor 54 b then receives the liquid slag from the first reactor, which can be processed further in the second reactor 54 b. This makes it possible to carry out further processing of the slag with greater degrees of freedom, since there is no need to take account of the liquid iron.
- FIG. 4 shows a schematic ternary diagram, which provides only an outline of the concentrations of the principal fractions of the slag for the cement industry.
- the fraction of CaO (calcium oxide) and MgO (magnesium oxide) is plotted.
- the fraction of SiO 2 (silicon oxide) is plotted.
- the fraction of Al 2 O 3 (aluminum oxide) and Fe 2 O 3 (iron oxide) is plotted.
- the gangue 46 contained in the iron oxide may have a broad spectrum of substance fractions.
- the CaO+MgO fraction may vary between around 10% to around 30%, while the SiO 2 fraction varies between around 30% and around 70% and also the Al 2 O 3 and Fe 2 O 3 fraction varies between around 5% and around 55%.
- the objective is to analyze the actual composition of the gangue and which substances must be added to the gangue in order to obtain a defined slag.
- compositions for slag sand 48 and Portland cement 50 are shown.
- a homogeneous slag is generated, fundamentally on the basis of the gangue, with this slag having the physical composition, for example, of slag sand or Portland cement. It must be borne in mind here, however, that other physical properties of the slag as well, such as viscosity or the formation of a sufficient glass phase on solidification, are retained.
- An advantage of the smelting furnace disclosed and of the corresponding method is that the existing limitation on slag composition to a composition characterized by a particularly low melting temperature is removed. It is now possible to operate the smelting furnace in principle without confinement of its degrees of freedom, in particular, but not limited to chemical, physical and mineralogical characteristics of the slag, both in the fixed time profile and in the time profile. Accordingly, the arrows in FIG. 4 indicate that, starting from the gangue 46 , any desired composition of the slag may be obtained.
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Abstract
A method is disclosed for generating slag having desired characteristics.
Description
- The invention pertains to a method for generating slag and for making controlled adjustments to its characteristics, for use as mineral building material, for example. The characteristics of the slag encompass the physical and chemical composition and also the mineralogical properties of the slag.
- In nature, iron is present only in the form of iron oxide. Pig iron is produced, for example, in blast furnaces. These are shaft furnaces operating on the countercurrent principle, where the charge—that is, lump ore, pellets or sinter together with coke as reducing agent and limestone and possibly further additives—is fed in at the top side and a flow of hot gases is passed through this charge from the bottom side. In this way, the feed material is steadily heated during the transient time. The substoichiometric combustion of the coke results in the formation of the reduction-capable gas carbon monoxide (CO), which reduces the iron oxides contained in the charge into iron; the CO may oxidize to carbon dioxide (CO2) in the process. Because of the temperatures prevailing at the bottom of the blast furnace, the iron is present in the liquid state.
- In the lower part of the smelting furnace, pig iron and slag are tapped off at periodic intervals. Rapid cooling of the smelting furnace slag, possibly leading to a glassy solidification, can be used to produce slag sand. Sand properties can be positively influenced by the milling-in of cement. Furthermore, by substituting the slag sand for cement clinker, the CO2 footprint of cement can be improved as well.
- The composition of the slag here is dictated substantially by the gangue in the iron ore, the limestone fraction, and secondary constituents and additives in the feed material.
- The problem which exists, however, is that the composition of the slag and hence also of the slag sand can in principle be different at every tapping if the feed materials alter. In this case it is still possible to influence the limestone fraction and the secondary constituents and additives, but not the amount and natural composition of the gangue in the iron oxide. This means that the precise final composition of the slag is unknown only when it is tapped off. Given that the materials remain in the smelting furnace for many hours, the possibilities for short-term adaptation to the composition of the slag by way of the feed material, if they exist at all, are limited. Furthermore, the generation of slag sand in the blast furnace is contingent on the formation, during the smelting procedure, of a eutectic which has a low melting point and can therefore be tapped off more rapidly.
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EP 1 354 969 B1 and EP 632 791 B1, then, show methods for admixing the slag post-tapping with additives to optimize the composition of the slag for the slag sand. The disadvantage of this method, however, is that the addition of the additives may cause the slag to cool down more quickly, so making it no longer possible for the additives to bind optimally with the slag. The greater the amount of additives admixed to the slag, the more rapid the cooling of the slag. A skewed composition of the slag may arise, with an accumulation of the additives in one region and a deficiency of the additives in another region. - DE 197 08 034 A1 discloses a method for producing liquid pig iron or liquid steel precursors.
EP 1 198 599 B1 discloses a method for slag conditioning with introduction of smelting residues.EP 1 627 084 B1 discloses a method for profitably utilizing slag. DE 103 40 880 A1 discloses a method and an apparatus for atomizing slag. DE 10 2020 205 493 A1 discloses a method for establishing a controlled slag phase in a smelting assembly. - Furthermore, direct reduction plants and electric arc furnaces/smelters are also known in principle. Not known, however, is an analysis of the slag and/or the intermediates for the purpose of optimized adjustment of the slag characteristics.
- The object of the present invention, therefore, is to create an improved concept for a method for generating slag and for adjusting the characteristics of the slag arising in the smelting furnace.
- The object is achieved by the subject matter of the independent claim. Further advantageous embodiments are the subject matter of the dependent claims.
- In accordance with the invention, a method is disclosed for generating slag of desired characteristics in the production of pig iron, with steps as follows: a) heating iron oxide in a first reactor, so that with a reducing agent present a majority of the iron oxide is reduced to iron and an iron-containing intermediate is formed. This is done using a direct reduction plant. As the end product of the direct reduction plant, the iron-containing intermediate is then present, and may also be referred to as sponge iron.
- b) Thereafter, the iron-containing intermediate is heated in a second reactor, to give pig iron and the slag. The heating takes place preferably in a smelter in a reducing atmosphere. Hence it is possible to obtain a slag having an iron fraction of less than 10%, preferably less than 7%, more preferably less than 4%, which can be used for the cement industry. Slag with a higher iron fraction cannot be used for the cement industry, for quality reasons.
- c) In a further step, which may also take place before or parallel to step b), the iron-containing intermediate and/or the slag which is deposited during the further heating of the iron-containing intermediate are/is analyzed. The iron-containing intermediate is taken for analysis at the end of the direct reduction plant, between direct reduction plant and smelter (i.e., in both cases, before the heating in the smelter) or in the smelter (i.e., during the heating). Additionally or alternatively, a sample of the slag heated to the final temperature may also be taken from the smelter.
- d1) Depending on the analysis, a property of an additive to be added to the iron-containing intermediate is determined in order to alter the composition of the slag. In other words, a sample is taken of the iron-containing intermediate and/or of the slag. Since in the iron-containing intermediate, the iron oxide is already present in a very far-reduced state, the characteristics of the later slag can already be determined very well from it. The analysis reflects the actual state of the slag.
- The intermediate may comprise, for example, pyrites, dolomite, ilmenite or bauxite, or the basic form of the oxidic compounds, or any desired combination of the stated substances. These substances are also referred to as adjuvants and they influence the properties of the slag. Hence it is advantageous for the slag to have good reception capability for extraneous substances, to have a suitable velocity (preferably between 1.05 Pa*s and 1.15 Pa*s (pascal times second)) and to have a temperature at which, as a result of the solidification, the slag breaks down into the appropriate particle size fraction and there is sufficient formation of glassy phase, and to have good binding capacity for cement production. The good reception capacity of the slag ensures effective reception of the additives and hence high homogeneity of the slag. The viscosity enables the slag to flow through the tapping hole. The temperature/the composition and also the binding capacity are relevant to the quality of the end product—for example, slag sand, Portland cement, or similar.
- The additive thus determined is introduced into the second reactor, such as the smelter, for example, during the heating of the slag, to give the slag of the desired characteristics. The desired characteristics are also referred to as target characteristics.
- d2) Additionally or alternatively, a control unit, for example, may recognize from the analysis that the slag requires a thermal treatment to give the slag having the desired characteristics, and may initiate the thermal treatment.
- The liquid metal and the slag can be tapped off through tapping holes in the smelter. After the slag has exited the tapping hole, it is quenched, preferably with water, and atomized and therefore granulated. The aim is to obtain more than 90% glassy solidification. After that, the granules are ready for further use. As a check, and in order to be able to correct any faulty assumptions, the final granules may also be analyzed to ascertain whether they have the desired properties.
- For example, by means of the analysis conducted in d1), a thermal treatment of the slag may also be derived, in particular a defined cooling rate to give the desired property of the slag.
- It is not possible to withdraw an iron-containing intermediate from a conventional blast furnace, nor to add the additive to the iron-containing intermediate in the conventional blast furnace. The only possibility in the conventional blast furnace is to introduce material at the start and to withdraw the slag and the pig iron at the end. If it is found that the slag does not have the correct composition, the composition can only be altered when the additive added at the start has reached the end. This may take between half a day and a whole day. Accordingly, the method proposed cannot be transposed to the blast furnace.
- A smelting furnace is disclosed for the generation of pig iron and slag having desired characteristics. The smelting furnace comprises a direct reduction plant which is configured to heat iron oxide so that with a reducing agent present a majority of the iron oxide is reduced to iron and an iron-containing intermediate is formed. The iron oxide is heated, for example, to a temperature of between 900° C. and 1100° C. The reducing agent, preferably hydrogen, which may be recovered, for example, from the electrolysis of water using regenerative energies (wind, water, solar) for the provision of the required power, for reducing CO2 emissions, may be heated to the necessary reaction temperature for the operation of the direct reduction plant, before being introduced into the direct reduction plant. The iron-containing intermediate is also referred to as sponge iron.
- Downstream of the direct reduction plant is a reactor arrangement. The reactor arrangement receives the iron-containing intermediate and heats it to give pig iron and slag.
- The reactor arrangement may comprise one reactor or a plurality of reactors. The reactor, or one reactor of the plurality of reactors, for heating the iron-containing intermediate may be an electric arc furnace or a smelter or an induction furnace. An electric arc furnace is an electrical furnace which heats a substance in an oxidizing atmosphere, typically discontinuously. Discontinuously means that a quantity of the substance is heated and the substance after the heating is withdrawn before a new amount of the substance is heated. A smelter is an electric furnace which heats a substance in a reducing atmosphere, typically continuously. Continuously means that a portion of the substance in the smelter is tapped off regularly, while the smelter is fed to new substance. Regularly, therefore, iron-containing intermediate is introduced into the smelter and, likewise regularly, portions of the pig iron and of the slag are tapped off. In a smelter, for example, a residual melt may be left which may be seen in turn as a starting point for the smelting of further substance. The smelter is also referred to as a melting-reduction furnace, low-shaft furnace or submerged arc furnace (SAF). In particular, terms such as open slag bath furnace (OSBF) are also customary.
- When the iron-containing intermediate is heated in a smelter, the temperature up to which the heating takes place is, for example, 1500° C. to 1600° C. if the slag is being used to produce slag sand. This is the temperature at which the slag is tapped off. For the production of other mineral building materials, the maximum slag temperature may also be higher, since in this case the eutectic of the slag is no longer attained. The temperature at which the iron is tapped off is somewhat lower and is, for example, between 1400° C. and 1500° C. In particular, therefore, the tapping temperature of the pig iron is, for example, between 80° C. and 120° C. lower than the tapping temperature of the slag. The heating of the melt and the presence of the reducing agent, such as carbon and/or hydrogen, for example, cause the iron to be further reduced, and so the iron fraction in the slag is lowered. The atmosphere, more particularly reducing atmosphere, in the smelter is obtained, for example, by the reaction of carbon, dissolved in sufficient quantity in the melt, with oxidic constituents of the intermediate, owing to the prevailing chemical/physical conditions, to give a reducing gas, for example. If carbon is not present in sufficient amount in the melt, this reducing atmosphere may be generated by supplying a reduction gas and/or reduction gas-forming substance.
- The smelting furnace further comprises an analysis unit which is configured to analyze the iron-containing intermediate and/or the slag. In particular, the analyzing may take place during tapping or by sampling before the tapping, or in situ. The analyzing may preferably take place online. The slag may be determined for the production of mineral building materials, such as for the production of slag sand or Portland cement, for example, by analysis of the concentration ratio of calcium, silicon, aluminum and iron. Furthermore, however, by means of the smelting furnace presented and of the corresponding production method, the production of any desired mineral building materials is possible. The mineral building materials may differ in their composition and in their properties from slag sand. For example, but not exclusively, the mineral building material may differ in its chemical and/or physical and/or mineralogical properties from conventional slag sand. The analysis unit may be a laboratory located in the vicinity of the smelting furnace, for the laboratory results to be utilized for rapid influencing of the product, in particular.
- Furthermore, the smelting furnace has a control unit which is configured, depending on an analytical result, to determine a property of the added additive so as to alter a composition of the slag (actual composition) and to obtain the slag with a desired composition (target composition). Additionally or alternatively, the control unit may also recognize whether the slag requires a thermal treatment to obtain the slag having the desired characteristics.
- The additive is understood to refer in particular to a mixture of different substances. Substances used may include pyrites, dolomite, ilmenite and bauxite. The selection of the substances, for example, is then regarded as a property of the additive. Furthermore, the fraction of the selected substances within the total amount of the additive may be viewed as a property of the additive. Moreover, the total amount of the additive or the amount of the selected substances may also be viewed as a property of the additive. The amount, for example, denotes the mass or the volume of the substance. Typically, however, the property of the additive encompasses not only the selection of the substances but also their respective fractions, i.e., the composition of the additive, and also the amount of the additive.
- The thermal treatment may arise from the analysis of the actual state of the slag or else the desired characteristics of the slag. The thermal treatment is, for example, the operation of a defined temperature curve of the reactor arrangement for heating or else cooling the slag. For the generation of slag sand, for instance, it is necessary to cool the slag very rapidly in order to obtain at least 90% glassy solidification. Different mineral building materials, however, may have different requirements with regard to a temperature profile.
- In other words, a further possibility for control or regulation, as well as the adding of the additive, is to introduce heat into the reactor arrangement or else remove heat in a target-oriented manner on the basis of the measurement results obtained using the analysis unit. This supply or removal of heat may be variable over time—that is, it may have the goal, for example, of pursuing a temperature profile for slag and/or melt that necessitates a supply of heat at certain times and a removal of heat at other times, and the leaving of the process to itself, in thermal terms, at still other times.
- By means of such a procedure, it is possible for example to set a goal temperature for slag and/or melt in order to influence properties of slag and/or melt in a goal-directed way. In addition to this establishment of an individual goal temperature, it is known that the properties of slags and melts may be influenced not only by individual temperatures but also by the traversal of temperature profiles in order to obtain or to avoid particular material phases. In the area of slag, this might include the cooling of the melt phase in the rotary kiln furnace during production of cement clinker, which is required to operate at a rate such that the tricalcium silicate does not break down into dicalcium silicate and free lime and the tricalcium aluminate crystallizes in a fine-grained form, but at the same time not so quickly that the melt phase undergoes glasslike solidification.
- The desired characteristics for the slag are the characteristics whereby a mineral building material, formed after the granulation of the slag, has a desired chemical composition and/or a desired physical property and/or a mineralogical property. In the case of slag sand, granulation encompasses, for example, the rapid cooling (quenching) and atomization of the slag after tapping. For different mineral building materials, a different thermal treatment may occur in order to obtain the granules. The desired characteristics of the slag, especially in terms of mineralogical phase formation, elution behavior, etc., may accordingly be selected such as to form, for example, slag sand or Portland cement or any other mineral building material.
- The smelting furnace disclosed, therefore, is a response to the concern that the current efforts to replace coke by hydrogen as a reducing agent, owing to the high CO2 emissions in steelmaking, mean that, as a result of the switchover to the direct reduction process, the production of slag sand will be lost—such production in Germany alone accounts annularly for around six million metric tons. The smelting furnace described, more specifically the first reactor, is therefore already designed for the direct reduction process as well, and can be operated with (natural) gas or, advantageously, with hydrogen as reducing agent. It also enables the smelting furnace to produce mineralogical building materials other than the conventional slag sand, as well.
- The idea is to use a direct reduction plant and a reactor arrangement with, for example, a smelter. In the first reactor, the iron oxide is reduced via direct reduction methods. The iron can then be present at the end of the direct reduction plant as an iron-containing intermediate in solid form, in the form of sponge iron, for example. In the reactor arrangement, the smelter for example, the iron-containing intermediate is then heated to the preset temperature at which the liquid iron is tapped off.
- The separation of the overall process into two method segments with two or more individual steps (essentially the shaft furnace with a porous bed of material in the upper part, and the melting region with liquid phases in the lower part) likewise increases the number of degrees of freedom for the design of the atmosphere in the smelting furnace. Whereas in the conventional process, owing to the narrow connection, this atmosphere cannot be chosen in practice independently, or can be so chosen only to a small extent, the possibility exists in the process disclosed here for the atmosphere to be freely chosen. Correspondingly, in principle, any desired gas composition may be chosen in order, in particular, to ensure optimal conditions for the goal-directed production of products from the slag, but in particular not exclusively in terms of their chemical, physical and mineralogical properties.
- As far as the analysis is concerned, there are diverse possibilities, which are described illustratively on the basis of the smelter as (part of) the reactor arrangement. During the heating, for example, no further iron-containing intermediate is added to the reactor arrangement, more particularly to the smelter. In that case, the characteristics of the future slag may be ascertained via analysis of the iron-containing intermediate. From this it is possible to ascertain for example, what physical composition the additive should have and what amount of the additive should be added to the reactor arrangement in order to obtain desired characteristics for the slag. It is, however, also possible to carry out cyclical tapping only of a part of the iron and/or of the slag, while, again cyclically, new iron-containing intermediate is added and hence a part of the slag or of the iron always remains in the reactor arrangement, more particularly in the smelter. On the assumption that the slag in the smelter already has the desired characteristics, the additive may also be determined on the basis of the analysis of the iron-containing intermediate. In other words, only the characteristics of the newly arrived slag fraction need be adjusted. Furthermore, however, for verification, it is also possible to determine the characteristics of the slag in the smelter and, in the event of deviations from the desired characteristics, to adapt them by addition of the additive.
- In other words, in the analysis, the analysis unit can determine actual characteristics of the iron-containing intermediate and/or the slag and compare them with desired target characteristics of the slag, and adjust the properties of the additive or the thermal treatment depending on the difference between actual composition and target composition.
- In the reactor arrangement, the additives are heated with the iron-containing intermediate and may therefore mix or bind fully with or to the slag. The result is a uniform slag having the desired characteristics.
- In exemplary embodiments, the reactor arrangement comprises a first reactor, preferably the smelter, and a second reactor. The first reactor receives the iron-containing intermediate and heats it, to give the iron and the slag. The second reactor receives the liquid slag and subjects it via the control unit to a further treatment, to give the desired characteristics of the slag. The further treatment by the control unit has already been comprehensively described and comprises the addition of the additive, adjusted in terms of its properties. Additionally or alternatively, the further treatment comprises a thermal treatment of the slag. In this case, the slag is adjusted to the desired characteristics only after the iron has been tapped off, so that the process of pig iron production does not need to be altered.
- In further exemplary embodiments, the reactor arrangement, preferably the first reactor or the smelter, has an opening for introducing raw material, especially furnace dust, into the reactor unit. In this way, the furnace dust swelled up and captured in the direct reduction plant may be introduced, or else any other raw materials, especially those which can be airborne. These raw materials need not necessarily be attained in production of iron; instead, raw materials (with the capacity to be airborne) from other industries, such as from clay production, for example, may also be added. In particular, the raw material may be processed, for example dried and/or granulated, before being introduced into the reactor arrangement. The characteristics of the slag are altered as a result and are analyzed by the analysis unit after the raw material has been added. The advantage of adding furnace dust is that the furnace dust contains a not inconsiderable fraction of bound iron (in the lower single-digit percentage range) which is currently lost in production of iron. Through the introduction of the furnace dust into the reactor unit, the iron it contains is likewise melted and is therefore not lost.
- Instead of furnace dust, any desired raw material may also, generally, be introduced into the reactor arrangement. If the raw material is too small, it may be granulated for greater ease of introduction into the reactor arrangement. The granulation or pelletizing of raw material is advantageous if it has airborne capability. A material is regarded as having airborne capability if its particle size is less than 5 mm, preferably less than 3 mm or less than 1.5 mm. Raw materials with airborne capability can also be introduced into the reactor arrangement, but only by means of a carrier gas, which, however, is typically unwanted in the reactor arrangement.
- In other words, a further advantage of the method is the use also of fine-grain feedstocks (raw material) in the new process. With the process customary at present, fine-grain feedstocks are carried by the gas stream in the bed material and so do not enter the melt. Accordingly, this dust is lost to production. In the process presented here, it is now possible, with circumvension of traversal through the upper part of the process, for the dust to be introduced directly into the smelting furnace, optionally mixed with other substances and/or already generally pretreated—for example, but not exclusively, by means of heat, comminution or agglomeration. The only limitation on the selection of such dusts fundamentally is that they do not detract from the quality of melt and/or slag to the point where it becomes unusable. It is possible accordingly to make practical use, for example, of dusts from the immediate environment of the iron and steelmaking process and also from the production of mineral building materials, for logistical reasons.
- Exemplary embodiments show that the control unit is configured to select the amount of the additive such that the slag has a basicity of 1 to 5.5, preferably of 1.13 to 2. This is advantageous for the generation of mineral building materials.
- In further exemplary embodiments, the second reactor is configured to atomize the slag to give atomized slag, the atomized slag having a particle size of 1 to 100 μm, preferably 1 to 40 μm. The atomizing enables rapid cooling of the slag, in order to obtain the required glassy solidification for production of slag sand, for example. The atomizing may take place in the second reactor as part of the thermal treatment.
- Further exemplary embodiments show that the second reactor generates a mineral building material, a binder for example. It is possible, for example, for the control unit, as the additive or as part of the additive, to introduce cement into the second reactor, the second reactor being configured to mix the atomized slag and the cement with one another, with the atomized slag being mixed with cement in a ratio of 36:64 to 95:5, preferably 60:40 to 80:20, to give the mineral building material having a 28-d standard strength of at least 30 N/mm2.
- Preferred exemplary embodiments of the present invention are elucidated below with reference to the attached drawings, in which:
-
FIG. 1 : contrasts the conventional blast furnace (FIG. 1 a ) with an exemplary embodiment of the smelting furnace (FIG. 1 b ), in each case in a schematic sectional representation; -
FIG. 2 : shows an exemplary embodiment of the smelting furnace fromFIG. 1 b; -
FIG. 3 : shows a further exemplary embodiment of the smelting furnace fromFIG. 1 b , which can also be combined with the exemplary embodiment fromFIG. 2 ; -
FIG. 4 : shows a schematic representation of a ternary diagram of the principal constituents of the slag for the cement industry. - Ahead of further elucidation below of exemplary embodiments of the present invention in detail, using the drawings, it is noted that identical, functionally alike or equivalent elements, objects and/or structures across the various figures have been provided with the same reference signs, and so the descriptions of these elements depicted in different exemplary embodiments can be interchanged with one another and/or applied to one another.
-
FIG. 1 contrasts aconventional blast furnace 20 a (FIG. 1 a ) with asmelting furnace 20 b (FIG. 1 b ) which comprises adirect reduction plant 21 a and areactor arrangement 21 b, represented here as a smelter. Both plants each have a 22 a, 22 b, through which components including the iron oxide to be smelted enter the blast furnace. In the case of the blast furnace, the coke may also be added via this route. The smelting process is divided into different zones. A preheatingmaterial feed 24 a, 24 b is followed by azone 26 a, 26 b, in which the major part of the reduction of the iron oxide to iron takes place. In the carbonizingreduction zone 28 a, 28 b, a portion of the iron becomes enriched with carbon. The zones described so far are located in thezone direct reduction plant 21 a of the smelting furnace. Below the carbonizing zone in the blast furnace, and in the smelter in the smelting furnace, there is also the smelting zone, in which the temperature is high enough for the iron to liquefy and separate from the likewise liquid slag. The liquid iron and the liquid slag may be withdrawn through tapping 32 a, 32 b, 32 b′.holes - The
blast furnace 20 a additionally has afeed 34 for hot blasts, while thedirect reduction plant 21 a has a 36 a, 36 b for a reduction gas, hydrogen or carbon monoxide for example. Thefeed smelter 21 b comprises amain opening 38, through which an iron-containing intermediate 39 passes from the direct reduction plant into thesmelter 21 b. Thesmelter 21 b additionally comprises anopening 40, through which an additive can be introduced into the smelter. If the additive is to contain different substances, there may be one opening provided per substance. Alternatively, the substances may be mixed beforehand to give the additive, and then enter the smelter through an opening in the form of a mixed additive. On the bottom of the smelter, furthermore, there is a pool ofslag 42 andiron 44. The openings, however, are advantageously designed such that thesmelter 21 b carries out the heating in the absence of air. This means that the direct reduction plant can be connected securely to the smelter so that the iron-containing intermediate enters the smelter without air contact. - Because the smelter is a separate assembly from the direct reduction plant, it is now possible, in contrast to the blast furnace, to withdraw a sample of the slag and/or of the iron-containing intermediate 39 directly in the smelter before the withdrawal of the slag. Alternatively, the sample may even be taken from the direct reduction plant itself. The sample can be analyzed for its characteristics in an
analysis unit 43. Based on the result of analysis, acontrol unit 45 ascertains the quality of the additive. Viasignal line 51 a, the control unit is able to produce the additive and introduce it into the reactor arrangement, more particularly the smelter. Additionally or alternatively, thecontrol unit 45 may also, via afurther signal line 51 a, set a temperature of the smelter. It is thus possible to carry out thermal treatment of the melt by operation of a predetermined temperature curve, for example. - The
smelting furnace 20 b has the advantage, in contrast to a direct reduction plant in combination with an electric arc furnace operating under an oxidizing atmosphere, for example, that the further processing operation of an iron works attached to the blast furnace can also be used for the smelting furnace. Hence the iron can be refined into steel in a converter. The liquid steel may be desulfurized in a ladle furnace and adjusted in its quality and then shaped by means of a continuous casting plant. -
FIG. 2 shows the representation of thesmelting furnace 20 b fromFIG. 1 b in an exemplary embodiment. The exemplary embodiment additionally comprises afeed 52 for raw material into the smelter. Thefeed 52 may be configured as areturn conduit 52 a from thedirect reduction furnace 21 a, to pass the raw material from the direct reduction furnace into the smelter. If the raw material is not directly suitable for being introduced into the smelter, it is also possible for it to be subjected to an aftertreatment beforehand. The blown introduction of the reduction gas has the effect in particular of swirling up furnace dust. This dust can be captured and optionally preprocessed (e.g., pressed to form pellets or filtered) and passed into the smelter. Additionally or alternatively, the feed comprises anexternal feed 52 b for raw material. There, for example, furnace dust collected on the iron works site, or else raw material from other industries, can be introduced into the smelter. -
FIG. 3 shows an alternative exemplary embodiment of thesmelting furnace 20 b fromFIG. 1 b . Here, thereactor arrangement 21 b has a two-stage construction. Afirst reactor 54 a, presently the smelter, already shown inFIG. 1 b andFIG. 2 , is supplemented by asecond reactor 54 b. Thesecond reactor 54 b then receives the liquid slag from the first reactor, which can be processed further in thesecond reactor 54 b. This makes it possible to carry out further processing of the slag with greater degrees of freedom, since there is no need to take account of the liquid iron. - Furthermore, it is also possible to combine the feed for the raw material from
FIG. 2 with the division of the reactor arrangement fromFIG. 3 . -
FIG. 4 shows a schematic ternary diagram, which provides only an outline of the concentrations of the principal fractions of the slag for the cement industry. On the bottom side of the triangle, the fraction of CaO (calcium oxide) and MgO (magnesium oxide) is plotted. On the left-hand side, the fraction of SiO2 (silicon oxide) is plotted. On the right-hand side, the fraction of Al2O3 (aluminum oxide) and Fe2O3 (iron oxide) is plotted. Thegangue 46 contained in the iron oxide may have a broad spectrum of substance fractions. For instance, illustratively, the CaO+MgO fraction may vary between around 10% to around 30%, while the SiO2 fraction varies between around 30% and around 70% and also the Al2O3 and Fe2O3 fraction varies between around 5% and around 55%. The objective, then, is to analyze the actual composition of the gangue and which substances must be added to the gangue in order to obtain a defined slag. Illustratively, compositions forslag sand 48 andPortland cement 50 are shown. In other words, by admixing an additive, which may comprise a plurality of substances at different concentrations, a homogeneous slag is generated, fundamentally on the basis of the gangue, with this slag having the physical composition, for example, of slag sand or Portland cement. It must be borne in mind here, however, that other physical properties of the slag as well, such as viscosity or the formation of a sufficient glass phase on solidification, are retained. - An advantage of the smelting furnace disclosed and of the corresponding method is that the existing limitation on slag composition to a composition characterized by a particularly low melting temperature is removed. It is now possible to operate the smelting furnace in principle without confinement of its degrees of freedom, in particular, but not limited to chemical, physical and mineralogical characteristics of the slag, both in the fixed time profile and in the time profile. Accordingly, the arrows in
FIG. 4 indicate that, starting from thegangue 46, any desired composition of the slag may be obtained. - Certain aspects have been described in connection with an apparatus. It should nevertheless be understood that these aspects also constitute a description of the corresponding method, and so a block or a component of an apparatus is also understood to be a corresponding method step or a feature of a method step. In analogy to this, aspects described in connection with one or as one method step also constitute a description of a corresponding block or detail or feature of a corresponding apparatus.
- The exemplary embodiments described above represent merely an illustration of the principles of the present invention. It will be appreciated that modifications and variations of the details and arrangements described herein will be clear to others in the art. The intention is therefore that the invention should be restricted solely by the scope of protection of the subsequent claims and not by the specific details presented herein on the basis of the description and the elucidation of the exemplary embodiments.
-
-
- 20 a blast furnace
- 20 b smelting furnace
- 21 a direct reduction plant
- 21 b reactor arrangement
- 22 material feed
- 24 preheating zone
- 26 reduction zone
- 28 carbonizing zone
- 32 tapping holes
- 34 feed for blasts
- 36 feed for reaction gas
- 38 main opening of the reactor arrangement
- 39 iron-containing intermediate
- 40 opening for adding the additive
- 42 slag
- 43 analysis unit
- 44 iron
- 45 control unit
- 46 gangue
- 48 slag sand
- 50 Portland cement
- 51 signal line of the control unit
- 52 feed for raw material
- 54 a first reactor
- 54 b second reactor
Claims (12)
1. A method for generating slag of desired characteristics in the production of pig iron, with steps as follows:
a) heating iron oxide in a direct reduction plant, so that with a reducing agent present a majority of the iron oxide is reduced to iron and an iron-containing intermediate is formed;
b) heating the iron-containing intermediate in a reactor arrangement, to give pig iron and the slag;
c) analyzing, via an analysis unit, the iron-containing intermediate and/or the slag which deposits during the further heating of the iron-containing intermediate;
at least one of: d1) determining a property of an additive to be added to the iron-containing intermediate during the heating, depending on the analysis, in order to alter the composition of the slag, and adding the additive during the heating, to give the slag of the desired characteristics; and/or
d2) recognizing that the slag requires a thermal treatment to give the slag having the desired characteristics, and initiating the thermal treatment.
2. The method as claimed in claim 1 , wherein the direct reduction plant comprises a feed for hydrogen as reducing agent.
3. The method as claimed in claim 2 , wherein the reactor arrangement comprises a smelter having a reducing atmosphere.
4. The method as claimed in claim 3 , wherein the direct reduction plant is configured to heat the iron oxide up to a temperature of between 900° C. and 1100° C.
5. The method as claimed in claim 4 , wherein an analysis unit is used which is configured during the analysis to determine an actual composition of the iron-containing intermediate and/or of the slag in the reactor unit and to compare it with a desired target composition of the slag and to adjust the properties of the additive depending on the difference between actual composition and target composition.
6. The method as claimed in claim 5 , wherein a control unit is used which is configured to determine, as property of the additive, an amount of the additive and a composition of the additive.
7. The method as claimed in claim 6 , wherein a control unit is used which is configured to take account, for the target characteristics of the slag, of any selection from the following features in order to alter the actual characteristics of the slag: a desired chemical composition of the granulated slag, a desired physical property of the granulated slag, a mineralogical property of the granulated slag.
8. The method as claimed in claim 7 , wherein the smelter has an opening for introducing raw material into the smelter; wherein an analysis unit is used which is configured to analyze the slag after the introduction of the raw material.
9. The method as claimed in claim 8 , wherein a control unit is used which is configured to select the amount of the additive such that the slag has a basicity of 1 to 5.5.
10. The method as claimed in claim 9 , wherein the reactor arrangement has a first reactor which is configured to receive and to heat the iron-containing intermediate to give the iron and the slag, and wherein the reactor arrangement has a second reactor which is configured to receive the slag from the first reactor; where a control unit is used which is configured to introduce the additive into the second reactor and/or to initiate the thermal treatment of the slag in the second reactor, to give the slag having the desired characteristics.
11. The method as claimed in claim 10 , wherein the second reactor is configured to atomize the slag to give atomized slag, the atomized slag having a particle size of 1 to 100 μm.
12. The method as claimed in claim 11 , wherein the second reactor is configured a mineral building material, more particularly a binder; wherein the control unit is configured to introduce cement, as part of the additive, into the second reactor; wherein the second reactor is configured to mix the atomized slag and the cement with one another, the atomized slag being mixed with cement in a ratio of 36:64 to 95:5, to give the mineral building material, whose 28-d standard strength is at least 30 N/mm2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102021204258.9 | 2021-04-28 | ||
| DE102021204258.9A DE102021204258A1 (en) | 2021-04-28 | 2021-04-28 | Melting furnace for producing pig iron and slag of a desired quality |
| PCT/EP2022/060867 WO2022229084A1 (en) | 2021-04-28 | 2022-04-25 | Method for producing slag having a desired quality |
Publications (1)
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| US20240376559A1 true US20240376559A1 (en) | 2024-11-14 |
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| US18/286,474 Pending US20240376559A1 (en) | 2021-04-28 | 2022-04-25 | Method for producing slag having a desired quality |
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| US (1) | US20240376559A1 (en) |
| EP (1) | EP4330438A1 (en) |
| JP (1) | JP2024515791A (en) |
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| CN (1) | CN117441031A (en) |
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| DE102023105797A1 (en) | 2023-03-09 | 2024-09-12 | Thyssenkrupp Steel Europe Ag | Method for operating an electric melter |
| EP4545502A1 (en) | 2023-10-27 | 2025-04-30 | ThyssenKrupp Steel Europe AG | Cement mixture and method for the production thereof |
| EP4650461A1 (en) | 2024-05-13 | 2025-11-19 | ThyssenKrupp Steel Europe AG | Method for processing slags |
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| DE2841697A1 (en) * | 1978-09-25 | 1980-04-10 | Mannesmann Ag | METHOD FOR PRODUCING STEEL FROM SPONGE OF IRON IN ELECTRIC OVENS |
| US5397376A (en) * | 1992-10-06 | 1995-03-14 | Bechtel Group, Inc. | Method of providing fuel for an iron making process |
| AT398419B (en) | 1993-01-26 | 1994-12-27 | Holderbank Financ Glarus | METHOD FOR PRODUCING CEMENT FROM METALLURGICAL SLAGS |
| JP3560677B2 (en) * | 1995-03-24 | 2004-09-02 | 日新製鋼株式会社 | Operating method of electric smelting furnace with reduced electrode consumption |
| AT405523B (en) | 1996-03-05 | 1999-09-27 | Voest Alpine Ind Anlagen | METHOD FOR THE PRODUCTION OF LIQUID PIPE IRON AND AT LEAST PARTLY REDUCED NON-FERROUS ORE, AND SYSTEM FOR IMPLEMENTING THE METHOD |
| JP3403093B2 (en) * | 1998-10-21 | 2003-05-06 | 三菱重工業株式会社 | Method and equipment for producing reduced iron |
| AT407644B (en) | 1999-06-08 | 2001-05-25 | Voest Alpine Ind Anlagen | METHOD FOR SLAG CONDITIONING AND APPARATUS THEREFOR |
| JP2001342510A (en) * | 2000-06-02 | 2001-12-14 | Nisshin Steel Co Ltd | Method for smelting metal |
| DE10215594A1 (en) | 2002-04-10 | 2003-10-30 | Thyssenkrupp Stahl Ag | Process for conditioning liquid blast furnace slag |
| US6875251B2 (en) * | 2002-05-15 | 2005-04-05 | Hatch Ltd. | Continuous steelmaking process |
| AT412283B (en) | 2003-05-16 | 2004-12-27 | Voest Alpine Ind Anlagen | METHOD FOR RECYCLING SLAG |
| DE10340880A1 (en) | 2003-09-04 | 2005-03-31 | Polysius Ag | Process for pulverizing slag from a blast furnace used during pig iron manufacture comprises adding an additional material to the slag after removing pig iron and before pulverizing |
| JP4981462B2 (en) * | 2007-01-22 | 2012-07-18 | 電気化学工業株式会社 | Salt-blocking cement mortar, concrete and its hardened body |
| JP2009132546A (en) * | 2007-11-29 | 2009-06-18 | Jfe Steel Corp | Method and apparatus for processing molten slag |
| DE102007061062B4 (en) * | 2007-12-14 | 2012-08-02 | Peiner Träger GmbH | Process for producing a steel melt containing up to 30% manganese |
| WO2011135485A1 (en) * | 2010-04-26 | 2011-11-03 | Louis Johannes Fourie | A method and apparatus for making low phosphorous iron |
| WO2014003123A1 (en) * | 2012-06-27 | 2014-01-03 | 新日鐵住金株式会社 | Steel slag reduction method |
| JP2015227733A (en) * | 2014-05-30 | 2015-12-17 | 新日鉄住金エンジニアリング株式会社 | Manufacturing facility of molten metal iron |
| ITUA20163986A1 (en) * | 2016-05-31 | 2017-12-01 | Tenova Spa | METHOD AND EQUIPMENT FOR THE PRODUCTION OF CAST IRON, CAST IRON PRODUCED ACCORDING TO THAT METHOD |
| JP2018178245A (en) * | 2017-04-05 | 2018-11-15 | 株式会社神戸製鋼所 | Pretreatment method of steelmaking raw material |
| CN212293639U (en) * | 2020-04-23 | 2021-01-05 | 钢铁研究总院 | A hydrogen metallurgy device |
| DE102020205493A1 (en) | 2020-04-30 | 2021-11-04 | Sms Group Gmbh | Process for making liquid pig iron from a DRI product |
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| DE102021204258A1 (en) | 2022-11-03 |
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